Synthetic navel orangeworm pheromone composition and methods relating to production of same

Abstract

One or more embodiments of the invention are directed to the synthetic methods for making lepidopteran pheromones including navel orangeworm pheromones. The synthetic methods involve novel, efficient, and environmentally benign steps and procedures.

1. A method for synthesizing a sex attractant pheromone of formula R 3 —R 7 —R 1 —Y′ (7) comprising:
 producing a compound of formula Y′—R 1 —X (2) in an oxidation reaction on a compound of formula Y—R 1 —X (1); 
 producing a compound of formula 
 
       
         
           
           
               
               
           
         
       
       in an O-alkylation reaction on said compound of formula (2); and
 producing a final compound of formula R 3 —R 7 —R 1 —Y′ (7) in a reduction reaction and a hydrolysis reaction on a compound of formula 
 
       
         
           
           
               
               
           
         
         wherein:
 X is halogen, 
 Y is —OH, 
 Y′ is ═O, 
 R 1  is [—CH 2 —] m , or alkyl, 
 R 3  is CH 3 —[CH 2 ] n —, or alkyl, 
 R 5  is [—C≡C—] p , or alkynyl, 
 R 6  is [—C≡C—] q , or alkynyl, 
 R 7  is —C═C—C═C—, alkenyl, or R 8 , 
 W is —O-alkyl, —O—R 3 , or —O—CH 2 —CH 3 , 
 R 8  is the geometric cis configuration represented by structure 
 
       
       
         
           
           
               
               
           
         
         
           R 9  is —CH 3 , or alkyl, 
           R 10  is ≡C (−) , carbon anion, or de-protonated carbon, 
           M is a metal, sodium, lithium, potassium, or magnesium, wherein M and R 10  together may form a salt, 
           m is independently 5, 6, 7, 8, 9, 10, 11 or 12, 
           n is independently 1, 2 or 3, 
           p is independently 1 or 2, and 
           q is independently 1 or 2. 
         
       
     
     
       2. The method of  claim 1 , wherein said oxidation reaction is an TEMPO oxidation. 
     
     
       3. The method of  claim 1 , wherein said oxidation reaction is a chromium-mediated oxidation. 
     
     
       4. The method of  claim 1 , wherein said O-alkylation reaction of is an O-Alkyl-C-alkoxy addition reaction. 
     
     
       5. The method of  claim 1 , wherein said reduction reaction and said hydrolysis reaction is an alkyne reduction and an acetal hydrolysis. 
     
     
       6. The method of  claim 5 , wherein said reduction reaction is a borane reduction reaction. 
     
     
       7. The method of  claim 1 , further comprising producing a compound of formula (6) by reacting said compound of formula (3) with a compound of formula R 3 —R 5 —R 10 -M (8b). 
     
     
       8. The method of  claim 7 , wherein said reacting of said compound of formula (3) with said compound of formula R 3 —R 5 —R 10 -M (8b) comprises a nucleophilic addition reaction. 
     
     
       9. The method of  claim 7 , further comprising producing said compound of formula R 3 —R 5 —R 10 -M (8b) by reacting a compound of formula R 9 —R 6 —R 9  (8a) using a triple bond migration rearrangement reaction. 
     
     
       10. The method of  claim 9 , wherein said triple bond migration rearrangement reaction is an isomerization reaction. 
     
     
       11. The method of  claim 7 , wherein:
 said compound of formula (1) is a halo substituted alkyl alcohol; 
 said compound of formula (2) is a halo substituted alkanal; 
 said compound of formula (3) is a halo substituted dialkoxy substituted alkyl; 
 said compound of formula (6) is a dialkoxy substituted diynyl; and 
 said compound of formula (8b) is a terminal alkyne. 
 
     
     
       12. The method of  claim 7 , wherein:
 said compound of formula (1) is 10-chlorodecan-1-ol; 
 said compound of formula (2) is 10-chlorodecanal; 
 said compound of formula (3) is 10-chloro-1,1-diethoxydecane; 
 said compound of formula (6) is 16,16-diethoxyhexadeca-3,5-diyne; 
 said compound of formula (8b) is 1,3-hexadiyne; and 
 said final compound of formula (7) is (Z,Z)-11,13-hexadecadien-1-al. 
 
     
     
       13. The method of  claim 9 , wherein said compound of formula (8a) is an internal alkyne. 
     
     
       14. The method of  claim 9 , wherein said compound of formula (8a) is 2,4-hexadiyne. 
     
     
       15. The method of  claim 1 , further comprising the steps of:
 producing a compound of formula 
 
       
         
           
           
               
               
           
         
       
       in an alkylation reaction on said compound of formula (3); and
 producing a compound of formula (6) by reacting said compound of formula (4) with a compound of formula R 3 —R 5 —X (5b). 
 
     
     
       16. The method of  claim 15 , wherein said alkylation reaction is an alkynyl-de-halogenation reaction. 
     
     
       17. The method of  claim 15 , wherein reacting said compound of formula (4) with a compound of formula R 3 —R 5 —X (5b) comprises a cycle of oxidative additions and reductive eliminations. 
     
     
       18. The method of  claim 15 , further comprising producing said compound of the formula (5b) by reacting a compound of the formula R 3 —R 4  (5a) using a substitution reaction. 
     
     
       19. The method of  claim 18 , wherein said substitution reaction is a halogenation.